Vat dye and process of making same.



UNITED STATEs n PE T OFFICE;

. ALBRECHT SOHMIDT AND ERNST BRYK, OF HOOHST-ON-THE MAIN, GERMANY, ASSIGNORS TO FARBWERKE VORM. MEISTER LUCIUS & BRllNING, OF HOCHST-ON-THE-MAIN, GER- MANY, A CORPORATION OF GERMANY. I

VAT DYE AND PROCESS OF MAKING SAME.

Specification 0t Letters Patent. Patented March 28, 1909.

Application filed May 22, 1907; Serial No. 875,125.

To all whom it may concern:

Be it known that ,we, ALBRECHT SCHMIDT, Ph. D., and ERNST BRYK, Ph. D., chemists, citizens of the Empires of Germany. and Austria-Hungary, res ectively, residing at Hochst-on-the-Main, ermany, have invented certain new and useful Improvements in Making Vat Dyestufis, of which the following is a specification.

- We have found a process of making vat dyestufls'by'treating with chlorsulfonic acid (SO HCl) such halogen substitution prod nets of arylthioglycolic acids as are not substituted in one ortho position to the S.CH COOH group, that is to say, thioglycolic acids of the general constitution:

wherein R R R means radicals, for instance, hydrogen, methyl, halogen, alkoxyl (CH,O, O,,H O) N0 Vat dyestufiis of the composition:

- hot dilute alkaliesand then with hot alcohol so as'to remove any unchanged parent material and byroducts. They are insoluble in water, alka ies and dilute acids and when treated with alkaline reducing agents, like hydrosulfite, they are dissolved in form of leuco-compounds, dyeing from such solutions (vats) cotton and wool very fast shades which vaty according to the kind, number and position of the substituents, as maybe seen from the accompanying table.

The above mentioned parent materials, the haloge'n-thioglycolic acids,.may be obtained according to known methods, for instance, from the corresponding halogen anilin by diazotizing an amin halogen substituted and not substituted in one ortho position,- by combining the diazo compound with a Xanthogenate and by treating the nanthogenate with chloracetic acid in alkaline solution, for instance,- in alcohol-alkaline solution. I

- Example I. 1 part by weight of chIorphe nylthiog ycolic acid n aon co onu obtained from o-chloranilin, is introduced while cooling into 1-2 volume parts of chlorsulfonic acid, whereby the temperature rises to about 35 C. It may be even stirred for a considerable time with stron er cooling. On the reaction being com lete t e mass is further worked up as descri ed above. The dy estuff thus obtained having the formula:

somooon 1 2 ci.o,n,, i 3

obtained, for instance, from ortho-chlormeta toluidin NH,: Cl: CH,=1: 2: 5, is introduced at ordinary temperature into 1% volume parts of chlorsulfonic acid, whereby the temperature rises to about 40 C. it is stirred until a decided green coloration occurs and the mass is worked up as de scribed heretofore. The dyestufi thus obtained having the formula:

o,H, o=o 0H2 3 S 3( p is a bluish-red powder, dyeing cotton and wool in the vat bluish-red tints.

Example III. 1 part by weight of chloranisylthioglycolic acid someoon 1 obtained, for instance, from chloranisidin NH,:C1:OCH 1 2 5 :2

is introduced into the above described chlorsulfonic acid. The mass then becomes red and on the reaction being complete it is worked up in the manner described above.

The dye stuff having the formula;

The condensation may also occur in presence of such'agents as accelerate 1t, for 1n-,

2 on3 (6)00 co e 063 2 I stance, borid acid and thelike.

' c,n c=c O.H, In this manner we have obtained vat dye- Cl 8 8 (5) stuffs by means of chlorsulfonic acid from is a dark violet powder, dyeing cotton and chlorarylthioglycolic acids, as shown in the wool in the vat very beautifu violet-blue following tab e: tints.-. 1 v I Chlorphenylthioglycolic acid S.CH,COOH Cl 1 4 .1 Violet-red on cotton H H H v.H H 1 3..l-- ---Re(i M H H (l v (I (l j 1 :-2 H 'H H Dichlorphenylthioglycolic acid S.CH,,CCOH Cl 1 2 4 Red-violet on cotton o H H l H (l U 1:4 H K H H If l H H U 1 z 2 :5 I -P Bluish red U U 1 f 1 :3 :.5 -Red on wool Chlortolylthioglycolic acid SCl- L COOH CH Cl 1 2 4---- Red-violet on cotton U H I I l K (K H u n u v u (0 u l 1 i u u u u :2 u u u k: x I 14 u u i u u o SCH CQOH :Cl :CH 1 :2 :5 -Red Bromphenylthiogly colic acid SC ILCCOH Br 1 4"- Red-violet on cotton I t l I ,y( l 1 :3 I H (l l I Chloranisylthioglycolic acid s.cH,oooH 01 =o :OH, 11 32 Chlor-p-xylylthioglycolic acid SCH COOH CH :Cl :CH 1 :2 :4 5 Red-violet on cott on Dichlor-m-tolylthioglycolic acid S.CH,,COOH:C1:ClzCI-I 1 :2 1 5 Red-violet on cotton Violet-blue on cotton Chlorphenetidylthioglycolic acid S,CH,COOH :Cl zOC H 1 :5 :2 -Violet-blue on cotton Having now described our invention, what we claim is:

1. The process herein described of making vat dyestuffs for cotton .and wool, which consists in treating with chlorsulfonic acid halogenarylthioglycolic acids of the type:

Halogen-QR, R R

S.0H .CO0H

wherein R R R mean hydro gen, halogen,-

wherein R and R mean hydrogen, halogen,

methyl, alkoxyl, and R halogen, methyl, alkoxyl, being insoluble in water, alkalies and dilute acids, li roin, alcohol and ether; soluble in hot nitro enzene with a violet-red color, in coldconcentrated sulfuric acid with a greenish color,vfrom which solution it is re recipitated unchanged by water, forming wl en treated with alkaline reducing agents, like hydrosulfite, a yellow vat solution and producing on porcelain a metallic stroke. In testimony, that we claim the foregoing as our invention, we have signed, our names in presence of/two subscribing witnesses.

ALBRECHT SCHMIDT.

ERNS'T BRYK. Witnesses:

JEAN GRUND, CARL GRUND. 

